U.S. patent number 10,214,420 [Application Number 15/520,031] was granted by the patent office on 2019-02-26 for method, system, and device for delivery of process gas.
This patent grant is currently assigned to RASIRC, Inc.. The grantee listed for this patent is RASIRC, Inc.. Invention is credited to Daniel Alvarez, Jr., Edward Heinlein, Russell J. Holmes, Christopher Ramos, Jeffrey Spiegelman.
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United States Patent |
10,214,420 |
Alvarez, Jr. , et
al. |
February 26, 2019 |
Method, system, and device for delivery of process gas
Abstract
A method and chemical delivery system and device are provided.
One method includes contacting a non-aqueous hydrazine solution
with a carrier gas and/or vacuum and delivering a gas stream
comprising hydrazine to a critical process or application. One
chemical delivery system and device includes a non-aqueous
hydrazine solution having a vapor phase that is in contact with a
carrier gas and/or vacuum. One device includes a chamber for
containing a liquid comprising at least one volatile process
chemical, such as a non-aqueous hydrazine solution, a hydrogen
peroxide solution, or another suitable process chemical, and a head
space from which the volatile can be drawn using a carrier gas
and/or vacuum. Another method useful in the present invention
involves drawing a process chemical from a device as a disclosed
herein using a carrier or vacuum and delivering the process
chemical to a critical process or application.
Inventors: |
Alvarez, Jr.; Daniel
(Oceanside, CA), Holmes; Russell J. (San Diego, CA),
Spiegelman; Jeffrey (San Diego, CA), Heinlein; Edward
(San Diego, CA), Ramos; Christopher (Bonita, CA) |
Applicant: |
Name |
City |
State |
Country |
Type |
RASIRC, Inc. |
San Diego |
CA |
US |
|
|
Assignee: |
RASIRC, Inc. (San Diego,
CA)
|
Family
ID: |
55761540 |
Appl.
No.: |
15/520,031 |
Filed: |
October 22, 2015 |
PCT
Filed: |
October 22, 2015 |
PCT No.: |
PCT/US2015/056887 |
371(c)(1),(2),(4) Date: |
April 18, 2017 |
PCT
Pub. No.: |
WO2016/065132 |
PCT
Pub. Date: |
April 28, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20170369315 A1 |
Dec 28, 2017 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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62067901 |
Oct 23, 2014 |
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62190578 |
Jul 9, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01B
21/16 (20130101); B01D 19/0031 (20130101); B01D
63/06 (20130101); B01D 19/0068 (20130101); B01D
2325/42 (20130101) |
Current International
Class: |
B01D
19/00 (20060101); C01B 21/16 (20060101); B01D
63/06 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2001047805 |
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Jul 2001 |
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WO |
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2013148262 |
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Oct 2013 |
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WO |
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Other References
PCT/US2015/056887 International Search Report dated Feb. 10, 2016.
cited by applicant.
|
Primary Examiner: Greene; Jason M
Attorney, Agent or Firm: Wagenknecht IP Law Group PC
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION(S)
This application is a 35 U.S.C. .sctn. 371 National Stage
application of International Application No. PCT/US2015/056887,
filed on Oct. 22, 2015, which claims priority to and the benefit
under 35 U.S.C. .sctn. 119(e) of U.S. Provisional Patent
Application Nos. 62/067,901, filed on Oct. 23, 2014, and
62/190,578, filed on Jul. 9, 2015, the disclosure of each of the
prior applications is considered part of and is incorporated herein
by reference in their entirety.
Claims
What is claimed is:
1. A method comprising: (a) providing a non-aqueous solution
comprising a process chemical in a device configured to contain a
liquid and a vapor phase, wherein the non-aqueous solution has a
vapor phase comprising an amount of anhydrous vapor of the process
chemical; (b) contacting a carrier gas or vacuum with the vapor
phase to form a gas stream; and (c) delivering the gas stream
formed in step (b) to a critical process or application, wherein
the process chemical is hydrazine or hydrogen peroxide, and wherein
at least one membrane is disposed in the device, the membrane being
configured to at least partially separate the vapor phase from the
non-aqueous solution.
2. The method of claim 1, further comprising changing the
concentration of at least one component of the vapor phase by
changing at least one of the following parameters: (a) the
temperature of the non-aqueous solution, (b) the pressure of the
non-aqueous solution, (c) the concentration of the non-aqueous
solution, (d) the temperature of the carrier gas, (e) the pressure
of the carrier gas or vacuum, and (f) the flow rate of the carrier
gas.
3. The method of claim 1, wherein the anhydrous vapor permeates the
membrane at a faster rate than any other component of the
non-aqueous solution.
4. The method of claim 1, wherein the membrane is an ion exchange
membrane.
5. The method of claim 1, further comprising removing contaminants
from the gas stream.
6. The method of claim 1, wherein the carrier gas is selected from
the group consisting of nitrogen, argon, hydrogen, clean dry air,
and helium.
7. The method of claim 1, further comprising changing the
concentration of at least one component of the vapor phase by
adding energy to the non-aqueous solution.
8. The method of claim 1, wherein the non-aqueous solution further
comprises a solvent selected from the group consisting of oligomers
of polyaniline, polypyrrole, polypyridine, and polyvinylalchohol,
wherein the viscosity of the solution is about 35 cp or less.
9. The method of claim 1, wherein the non-aqueous solution further
comprises a solvent selected from monoglyme, diglyme, triglyme,
higlyme, tetraglyme, Polyglycol DME 200, Polyglycol DME 250,
Polyglycol DME 500, Polyglycol DME 1000, Polyglycol DME 2000,
hexamethylphosoramide or hexamethylenetetramine.
10. The method of claim 1, wherein the non-aqueous solution further
comprises a PEGylated solvent, wherein the PEGylated solvent is a
liquid when at a temperature of about 25.degree. C.
11. The method of claim 1, wherein the non-aqueous solution further
comprises poly(ethylene glycol) dimethyl ether.
12. The method of claim 1, wherein the non-aqueous solution is a
non-aqueous hydrazine solution comprising from about 25% to about
69% by weight of hydrazine.
13. The method of claim 12, wherein the non-aqueous hydrazine
solution comprises from about 65% to about 69% by weight of
hydrazine.
14. The method of claim 1, wherein the non-aqueous solution
contains less than 0.1% water.
15. The method of claim 1, wherein the concentration of anhydrous
vapor delivered in the gas stream is stable to within about 5% of
the average concentration delivered.
16. A chemical delivery system comprising: (a) a device configured
to contain a liquid and a vapor phase; (b) a non-aqueous solution
comprising a process chemical provided in the device, wherein the
non-aqueous solution has a vapor phase comprising an amount of
anhydrous vapor of the process chemical; (c) a carrier gas or
vacuum in fluid contact with the vapor phase and configured to form
a gas stream containing the anhydrous vapor, wherein the process
chemical is hydrazine or hydrogen peroxide and wherein the device
has an outlet configured to deliver the gas stream to a critical
process or application, and wherein the device includes at least
one membrane configured to at least partially separate the vapor
phase from the non-aqueous solution.
17. The chemical delivery system of claim 16, further comprising
one or more components configured to change the concentration of at
least one component of the vapor phase by changing at least one of
the following parameters: (a) the temperature of the non-aqueous
solution, (b) the pressure of the non-aqueous solution, (c) the
concentration of the non-aqueous solution, (d) the temperature of
the carrier gas, (e) the pressure of the carrier gas or vacuum, and
(f) the flow rate of the carrier gas.
18. The chemical delivery system of claim 16, wherein the membrane
is an ion exchange membrane.
19. The chemical delivery system of claim 16, wherein the carrier
gas is selected from the group consisting of nitrogen, argon,
hydrogen, clean dry air, and helium.
20. The chemical delivery system of claim 16, wherein the device
further comprises a component configured to add energy to the
non-aqueous hydrazine solution.
21. The chemical delivery system of claim 16, wherein the
non-aqueous solution further comprises a solvent.
22. The chemical delivery system of claim 21, wherein the solvent
is poly(ethylene glycol) dimethyl ether.
23. The chemical delivery system of claim 16, wherein the
non-aqueous solution is a non-aqueous hydrazine solution comprising
from about 25% to about 69% by weight of hydrazine.
24. A device comprising: (a) a housing comprising an inlet port and
an outlet port, the housing being configured to contain a liquid
and a vapor phase; (b) a tubular membrane having a first end and a
second end, the tubular membrane being disposed within the housing
and configured to be in contact with the liquid when present in the
housing, wherein the first end is in fluid communication with the
inlet port; (c) a splash guard disposed within the housing and in
fluid communication with the outlet port, wherein the splash guard
is configured to retain the second end of the tubular membrane
within a headspace of the housing and to prevent liquid from
exiting the housing.
25. The device of claim 24, wherein the tubular membrane is an ion
exchange membrane.
26. The method of claim 14, wherein the non-aqueous solution
contains less than 0.01% water.
27. The method of claim 26, wherein the non-aqueous solution
contains less than 0.001% water.
28. The method of claim 15, wherein the concentration of anhydrous
vapor delivered in the gas stream is stable to within about 3% of
the average concentration delivered.
Description
TECHNICAL FIELD
Methods, systems, and devices for the vapor phase delivery of high
purity process gases in micro-electronics and other critical
process applications.
BACKGROUND
Various process gases may be used in the manufacturing and
processing of micro-electronics. In addition, a variety of
chemicals may be used in other environments demanding high purity
gases, e.g., critical processes, including without limitation
microelectronics applications, wafer cleaning, wafer bonding,
photolithography mask cleaning, atomic layer deposition, chemical
vapor deposition, flat panel displays, disinfection of surfaces
contaminated with bacteria, viruses and other biological agents,
industrial parts cleaning, pharmaceutical manufacturing, production
of nano-materials, power generation and control devices, fuel
cells, power transmission devices, and other applications in which
process control and purity are critical considerations. In those
processes, it is necessary to deliver specific amounts of certain
process gases under controlled operating conditions, e.g.,
temperature, pressure, and flow rate.
For a variety of reasons, gas phase delivery of process chemicals
is preferred to liquid phase delivery. For applications requiring
low mass flow for process chemicals, liquid delivery of process
chemicals is not accurate or clean enough. Gaseous delivery would
be desired from a standpoint of ease of delivery, accuracy and
purity. One approach is to vaporize the process chemical component
directly at or near the point of use. Vaporizing liquids provides a
process that leaves heavy contaminants behind, thus purifying the
process chemical. Gas flow devices are better attuned to precise
control than liquid delivery devices. Additionally,
micro-electronics applications and other critical processes
typically have extensive gas handling systems that make gaseous
delivery considerably easier than liquid delivery. However, for
safety, handling, stability, and/or purity reasons, many process
gases are not amenable to direct vaporization.
There are numerous process gases used in micro-electronics
applications and other critical processes. Ozone is a gas that is
typically used to clean the surface of semiconductors (e.g.,
photoresist stripping) and as an oxidizing agent (e.g., forming
oxide or hydroxide layers). One advantage of using ozone gas in
micro-electronics applications and other critical processes, as
opposed to prior liquid-based approaches, is that gases are able to
access high aspect ratio features on a surface. For example,
according to the International Technology Roadmap for
Semiconductors (ITRS), current semiconductor processes should be
compatible with a half-pitch as small as 20-22 nm. The next
technology node for semiconductors is expected to have a half-pitch
of 10 nm, and the ITRS calls for <7 nm half-pitch in the near
future. At these dimensions, liquid-based chemical processing is
not feasible, because the surface tension of the process liquid
prevents it from accessing the bottom of deep holes or channels and
the corners of high aspect ratio features. Therefore, ozone gas has
been used in some instances to overcome certain limitations of
liquid-based processes, because gases do not suffer from the same
surface tension limitations. Plasma-based processes have also been
employed to overcome certain limitations of liquid-based processes.
However, ozone- and plasma-based processes present their own set of
limitations, including, inter alia, cost of operation, insufficient
process controls, undesired side reactions, and inefficient
cleaning.
Other problems relate to the temperature necessary for successful
deposition. With respect to silicon nitride (SiN) for example,
ammonia (NH.sub.3) is currently often used at temperatures in
excess of 500.degree. C. or even 600.degree. C. It is expensive to
maintain such high temperatures for deposition and it would be
preferable to deposit at lower temperatures. In addition, new
semiconductor device technologies have stringent thermal budgets,
which inhibit the use of elevated temperatures over 400.degree. C.
Hydrazine (N.sub.2H.sub.4) presents an opportunity to explore lower
temperatures in part because of the favorable thermodynamics of
hydrazine resulting in lower deposition temperatures and a
spontaneous reaction to form nitrides. Although reported in the
literature (Burton et al. J. Electrochem. Soc., 155(7) D508-D516
(2008)), hydrazine usage has not been adopted commercially due to
the serious safety concerns with using hydrazine. Substituted
hydrazines suffer from the drawback of leading to unwanted carbon
contamination. Thus, there is a need to develop a safer method for
using hydrazine for either deposition processes or for delivery to
other critical process applications.
The gas phase use of hydrazine has been limited by safety,
handling, and purity concerns. Hydrazine has been used for rocket
fuel and can be very explosive. Semiconductor industry protocol for
safe handling of this material is very limited. Therefore, a
technique is needed to overcome these limitations and,
specifically, to provide substantially water-free gaseous hydrazine
suitable for use in micro-electronics and other critical process
applications.
Similarly, as explained in PCT Publication No. 2014014511 by
Rasirc, Inc., which is hereby incorporated by reference herein, the
gas phase use of hydrogen peroxide in critical process applications
has been of limited utility, because highly concentrated hydrogen
peroxide solutions present serious safety and handling concerns and
obtaining high concentrations of hydrogen peroxide in the gas phase
has not been possible using existing technology.
SUMMARY OF CERTAIN EMBODIMENTS
Methods, systems, and devices for delivering a substantially
water-free process gas stream, particularly a hydrazine-containing
gas stream, are provided. The methods, systems, and devices are
particularly useful in micro-electronics applications and other
critical processes. Generally, the methods comprise (a) providing a
non-aqueous hydrazine solution having a vapor phase comprising an
amount of hydrazine vapor; (b) contacting a carrier gas or vacuum
with the vapor phase; and (c) delivering a gas stream comprising
substantially water-free hydrazine to a critical process or
application. In many embodiments, the amount of hydrazine in the
vapor phase is sufficient to provide hydrazine directly to a
critical process or application without further concentrating or
processing the hydrazine-containing gas stream. In many
embodiments, the non-aqueous hydrazine solution includes a
stabilizer. In certain embodiments, the methods further include
removing one or more stabilizers from the gas stream. By adjusting
the operating conditions of the methods, e.g., the temperature and
pressure of the carrier gas or vacuum, the concentration of the
hydrazine solution, and the temperature and pressure of the
hydrazine solution, hydrazine can be precisely and safely delivered
as a process gas. In certain embodiments, the amount of hydrazine
in the vapor phase and delivered to the critical process or
application can be controlled by adding energy to the hydrazine
solution, e.g., thermal energy, rotational energy, or ultrasonic
energy. In many embodiments of the invention, the non-aqueous
hydrazine is neat hydrazine or hydrazine that is substantially free
of water.
Systems and devices for delivering hydrazine using the methods
described herein are also provided. Generally, the systems and
devices comprise (a) a non-aqueous hydrazine solution having a
vapor phase comprising an amount of hydrazine vapor; (b) a carrier
gas or vacuum in fluid contact with the vapor phase; and (c) an
apparatus for delivering a gas stream comprising hydrazine to a
critical process or application. In many embodiments, the
non-aqueous hydrazine solution includes one or more stabilizers. In
certain embodiments, the systems and devices further include an
apparatus for removing one or more stabilizers from the gas stream.
In many embodiments, the amount of hydrazine in the vapor phase is
sufficient to provide hydrazine directly to a critical process or
application without further concentrating or processing the
hydrazine-containing gas stream. In certain embodiments, the
apparatus for delivering a gas stream comprising hydrazine is an
outlet of a head space, containing the vapor phase, that is
connected directly or indirectly to a micro-electronics application
or other critical process system, allowing the hydrazine containing
gas stream to flow from the head space to the application or
process in which it will be used. The hydrazine delivery assembly
(HDA) described herein is one such device. By adjusting the
operating conditions of the systems and devices, e.g., the
temperature and pressure of the carrier gas or vacuum, the
concentration of the hydrazine solution, and the temperature and
pressure of the hydrazine solution, hydrazine can be precisely and
safely delivered as a process gas. In certain embodiments, the
amount of hydrazine in the vapor phase and delivered to the
critical process or application can be controlled by adding energy
to the hydrazine solution, e.g., thermal energy, rotational energy,
or ultrasonic energy.
Many of the embodiments of the methods, systems, and devices
disclosed herein utilize a membrane in contact with the
hydrazine-containing solution. The use of the membrane has safety
advantages. In certain embodiments, the membrane wholly or
partially separates the hydrazine-containing solution from the
hydrazine-containing vapor phase. By eliminating access between the
vapor phase and the liquid phase, a sudden decomposition in the
vapor phase of the hydrazine would be limited and not cause a
corresponding decomposition in the liquid phase due to the presence
of the membrane.
Also disclosed herein are devices for containing a liquid
comprising a volatile chemical or chemical composition (e.g.,
hydrazine, hydrogen peroxide, water, alcohols, amines, or ammonium
hydroxide), wherein the device comprises a head space where vapor
comprising the chemical or composition is accessible as a process
gas to be incorporated into a process gas stream. The process gas
stream comprising the chemical or composition is typically
delivered to a critical process application. In certain
embodiments, the device comprises (a) a chamber containing a liquid
comprising a volatile chemical or chemical composition, (b) a head
space comprising a vapor phase that includes the volatile chemical
or chemical composition in the gas phase, (c) a inlet port through
which a carrier gas stream can enter the chamber, and (d) a
protected outlet port through which a process gas stream comprising
carrier gas and the volatile chemical or chemical composition can
exit the head space. In certain embodiments, the head space is a
portion of the chamber. In certain alternative embodiments, the
head space is distinct from the chamber and in fluid communication
with the chamber to allow the volatile chemical or chemical
composition in the gas phase to move from the chamber into head
space. In many embodiments, a membrane facilitates the transfer of
the volatile chemical or chemical composition from the liquid into
the gas phase. The configuration of the membrane may vary according
to the particular application and process design. In some
embodiments, the membrane wholly or partially separates the liquid
from the head space. In certain embodiments, the membrane comprises
a tube connected to the inlet port such that all or a portion of
the carrier gas travels through the membrane. In such embodiments,
the membrane tube may also travel through a portion of the liquid
in the chamber and terminate in the head space. The protected
outlet port comprises an apparatus to ensure that the volatile
chemical or chemical composition entering the exit port is
substantially in the gas phase, i.e., substantially free of liquid
phase material, such as droplets, mists, or fogs.
The methods, systems, and devices described herein are generally
applicable to a wide variety of process gas streams, particularly
non-aqueous hydrazine solutions wherein the hydrazine solutions
contain non-aqueous components.
In certain embodiments, the solution comprises substantially pure
hydrazine, meaning hydrazine in which no other chemicals are
deliberately included but allowing for incidental amounts of
impurities. In certain embodiments, the solution comprises from
about 5% to about 99% by weight of hydrazine, or from about 90% to
about 99%, from about 95% to about 99%, from about 96% to about
99%, from about 97% to about 99%, from about 98% to about 99%, or
from about 99% to about 100% by weight of hydrazine, with the
remaining components comprising solvents and/or stabilizers. In
some embodiments, the solution comprises hydrazine at
concentrations greater than 99.9% purity and, in some embodiments,
the solution comprises hydrazine at concentrations of greater than
99.99%. Selection of an appropriate non-aqueous hydrazine solution
will be determined by the requirements of a particular application
or process.
In certain embodiments, the non-aqueous hydrazine solution
comprises, in addition to hydrazine, one or more suitable solvents.
For example, the non-aqueous hydrazine solution may comprise a
PEGylated solvent, wherein the PEGylated solvent is a liquid when
at a temperature of about 25.degree. C. The term "PEGylated
solvent" refers to a solvent containing a covalently attached
poly(ethylene glycol) moiety. One exemplary PEGylated solvent is
poly(ethylene glycol) dimethyl ether. In some embodiments, the
suitable solvent is selected from low molecular weight polymers or
oligomers of polyaniline, polypyrrole, polypyridine or
polyvinylalchohol. A low molecular weight polymer is one such that
when combined with hydrazine, the combined solution has a viscosity
of about 35 centipoises (cp) or less. Other examples of solvents
include glymes such as monoglyme, diglyme, triglyme, higlyme, and
tetraglyme. Further examples include a range of PEGylated dimethyl
ethers such as Polyglycol DME 200, Polyglycol DME 250, Polyglycol
DME 500, Polyglycol DME 1000, or Polyglycol DME 2000. Still other
solvents include hexamethylphosoramide and hexamethylenetetramine.
In some embodiments, the non-aqueous hydrazine solution comprises
from about 30% to about 69% by weight and ranges in between
including between about 65% to about 69% by weight of hydrazine.
The remainder of the solution may comprise, for example, one or
more PEGylated solvents such as poly(ethylene glycol) dimethyl
ether. For instance, the hydrazine solution may comprise from about
32% to 35% by weight of PEGylated solvent such as poly(ethylene
glycol) dimethyl ether or other suitable solvents. In other
embodiments, less than about 65% hydrazine is used and more than
about 35% of a PEGylated solvent such as poly(ethylene glycol)
dimethyl ether is used such as Polyglycol DME 250.
The methods, systems, and devices provided herein can employ a
variety of membranes. The membrane is typically a selectively
permeable membrane, particularly a substantially gas-impermeable
membrane, e.g., a perfluorinated ion exchange membrane, such as a
NAFION.RTM. membrane. In certain embodiments, the NAFION.RTM.
membrane may be chemically treated e.g., with an acid, base, or
salt to modify its reactivity. For example, in certain embodiments,
the NAFION.RTM. membrane may be treated in a way to form the
ammonium species. By using certain selectively permeable membranes,
which typically are substantially gas-impermeable membranes and
specifically NAFION.RTM. membranes and its derivatives, the
concentration of the hydrazine gas in the resultant gas stream may
be altered relative to the hydrazine concentration that would be
obtained directly from the vapor of the hydrazine solution in the
absence of a membrane. In certain embodiments, the hydrazine gas
concentration is amplified (i.e., higher than) the concentration
that would be expected from the vapor of the hydrazine solution
absent the membrane. Preferably, the concentration of hydrazine is
amplified using the methods, systems, and devices disclosed
herein.
In another embodiment, the membrane is a copolymer of
tetrafluroethylene and sulfonyl fluoride vinyl ether. One such
example of such a membrane can be made from Aquivon.RTM. which is
sourced from Solvay. A specific Aquivon.RTM. polymer is known as
P98S and is provided as pellets.
The methods, systems, and devices provided herein may further
comprise removing one or more components from the hydrazine
containing gas stream to produce a purified hydrazine containing
gas stream, e.g., using a device that selectively or
non-selectively removes components from the gas stream. Preferred
devices would be devices that substantially remove a non-reactive
process gas from the hydrazine containing gas stream, while the
amount of hydrazine in the gas stream is relatively unaffected. For
example, a device may remove any non-aqueous solvents or
stabilizers from the gas stream, including without limitation any
traces of water or non-aqueous solvents. For example, the devices
may further comprise a purifier positioned downstream of the head
space. Particularly preferred purifier devices are membrane
contactors, molecular sieves, activated charcoal and other
adsorbents, if they have the desired characteristics to meet the
application or process requirements. A preferred characteristic of
the gas removal device is the ability to remove certain
component(s) in a relatively selective manner while allowing the
remaining component(s) to remain in the hydrazine gas stream
relatively unaffected.
The systems and devices provided herein may further comprise
various components for containing and controlling the flow of the
gases and liquids used therein. For example, the systems and
devices may further comprise mass flow controllers, valves, check
valves, pressure gauges, regulators, rotameters, and pumps. The
systems and devices provided herein may further comprise various
heaters, thermocouples, and temperature controllers to control the
temperature of various components of the devices and steps of the
methods.
Additional objects and advantages of the invention will be set
forth in part in the description which follows, and in part will be
obvious from the description, or maybe learned by practice of the
invention. The objects and advantages of the invention will be
realized and attained by means of the elements and combinations
particularly pointed out in the embodiments and claims.
It is to be understood that both the foregoing general description
and the following detailed description are exemplary and
explanatory only and are not restrictive of the invention.
The accompanying drawings, which are incorporated in and constitute
a part of this specification, illustrate several embodiments of the
invention and, together with the description, serve to explain the
principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a diagram illustrating a part of a membrane assembly
useful in certain embodiments of the present invention.
FIG. 1B is a diagram illustrating an embodiment of a hydrazine
delivery assembly (HDA) according to certain embodiments of the
present invention.
FIG. 2A is a cross-sectional view of an embodiment of an HDA
according to certain embodiments of the present invention.
FIG. 2B is a cross-sectional view of an embodiment of an HDA
according to certain embodiments of the present invention.
FIG. 3 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
FIG. 4 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
FIG. 5 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
FIG. 6 is a diagram illustrating a membrane assembly and HDA
according to certain embodiments of the present invention.
FIG. 7 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
FIG. 8 is a chart depicting hydrazine gas concentration and
temperature over time according to an embodiment of the present
invention, using substantially pure hydrazine as a liquid
source.
FIG. 9 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
FIG. 10 is a chart depicting hydrazine gas concentration and
temperature over time according to an embodiment of the present
invention, using anhydrous 98% hydrazine as a liquid source.
FIG. 11 is a chart depicting hydrazine gas concentration and
temperature over time according to an embodiment of the present
invention, using 65% hydrazine in poly(ethylene glycol) dimethyl
ether as a liquid source.
FIG. 12 is a diagram illustrating an HDA according to certain
embodiments of the present invention.
FIG. 13 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention.
DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS
The term "process gas" as used herein is a broad term, and is to be
given its ordinary and customary meaning to a person of ordinary
skill in the art (and is not to be limited to a special or
customized meaning), and refers without limitation to a gas that is
used in an application or process, e.g., a step in the
manufacturing or processing of micro-electronics and in other
critical processes. Exemplary process gases are reducing agents,
oxidizing agents, inorganic acids, organic acids, inorganic bases,
organic bases, and inorganic and organic solvents. A preferred
process gas is hydrazine.
The term "reactive process gas" as used herein is a broad term, and
is to be given its ordinary and customary meaning to a person of
ordinary skill in the art (and is not to be limited to a special or
customized meaning), and refers without limitation to a process gas
that chemically reacts in the particular application or process in
which the gas is employed, e.g., by reacting with a surface, a
liquid process chemical, or another process gas.
The term "non-reactive process gas" as used herein is a broad term,
and is to be given its ordinary and customary meaning to a person
of ordinary skill in the art (and is not to be limited to a special
or customized meaning), and refers without limitation to a process
gas that does not chemically react in the particular application or
process in which the gas is employed, but the properties of the
"non-reactive process gas" provide it with utility in the
particular application or process.
The term "carrier gas" as used herein is a broad term, and is to be
given its ordinary and customary meaning to a person of ordinary
skill in the art (and is not to be limited to a special or
customized meaning), and refers without limitation to a gas that is
used to carry another gas through a process train, which is
typically a train of piping. Exemplary carrier gases are nitrogen,
argon, hydrogen, oxygen, CO2, clean dry air, helium, or other gases
that are stable at room temperature and atmospheric pressure.
The term "head space" as used herein is a broad term, and is to be
given its ordinary and customary meaning to a person of ordinary
skill in the art (and is not to be limited to a special or
customized meaning), and refers without limitation to a volume of
gas in fluid contact with a hydrazine solution that provides at
least a portion of the gas contained in the head space. There may
be a permeable or selectively permeable barrier wholly or partially
separating the head space that is optionally in direct contact with
the hydrazine solution. In those embodiments where the membrane is
not in direct contact with the hydrazine solution, more than one
head space may exist, i.e. a first head space directly above the
solution that contains the vapor phase of the solution and a second
head space separated from the first head space by a membrane that
only contains the components of the first space that can permeate
the membrane, e.g., hydrazine. In those embodiments with a
hydrazine solution and a head space separated by a substantially
gas-impermeable membrane, the head space may be located above,
below, or on any side of the hydrazine solution, or the head space
may surround or be surrounded by the hydrazine solution. For
example, the head space may be the space inside a substantially
gas-impermeable tube running through the hydrazine solution or the
hydrazine solution may be located inside a substantially
gas-impermeable tube with the head space surrounding the outside of
the tube.
The term "substantially gas-impermeable membrane" as used herein is
a broad term, and is to be given its ordinary and customary meaning
to a person of ordinary skill in the art (and is not to be limited
to a special or customized meaning), and refers without limitation
to a membrane that is relatively permeable to other components that
may be present in a gaseous or liquid phase, e.g., hydrazine, but
relatively impermeable to other gases such as, but not limited to,
hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide,
hydrogen sulfide, hydrocarbons (e.g., ethylene), volatile acids and
bases, refractory compounds, and volatile organic compounds.
The term "ion exchange membrane" as used herein is a broad term,
and is to be given its ordinary and customary meaning to a person
of ordinary skill in the art (and is not to be limited to a special
or customized meaning), and refers without limitation to a membrane
comprising chemical groups capable of combining with ions or
exchanging with ions between the membrane and an external
substance. Such chemical groups include, but are not limited to,
sulfonic acid, carboxylic acid, sulfonamide, sulfonyl imide,
phosphoric acid, phosphinic acid, arsenic groups, selenic groups,
phenol groups, and salts thereof.
The term "permeation rate" as used herein is a broad term, and is
to be given its ordinary and customary meaning to a person of
ordinary skill in the art (and is not to be limited to a special or
customized meaning), and refers without limitation to the rate at
which a specific chemical, e.g., hydrazine, or a chemical
composition a permeates a membrane. The permeation rate may be
expressed as an amount of the chemical or composition of interest
that permeates a particular surface area of membrane during a
period of time, e.g., liters per minute per square inch
(L/min/in.sup.2).
The term "non-aqueous solution" as used herein is a broad term, and
is to be given its ordinary and customary meaning to a person of
ordinary skill in the art (and is not to be limited to a special or
customized meaning), and refers to a solution comprising hydrazine
and optionally other components and containing less than 10% by
weight of water. Exemplary non-aqueous solutions include those
containing less than 2%, 0.5%, 0.1%, 0.01%, 0.001% or less
water.
The term "stabilizer" as used herein is a broad term, and is to be
given its ordinary and customary meaning to a person of ordinary
skill in the art (and is not to be limited to a special or
customized meaning), and refers to a chemical that prevents the
decomposition or reaction of process chemical, such as hydrazine or
hydrogen peroxide. In certain embodiments, the stabilizer is
non-volatile and is not present in the vapor phase in more than an
insubstantial amount. In certain embodiments, the stabilizer can be
removed from the process gas stream by exposing the process gas
stream to an adsorbent or passing the process gas stream through a
cold trap. In certain embodiments that include a membrane
separating the non-aqueous hydrazine solution from the vapor phase,
the stabilizer may not permeate the membrane.
The methods, systems, and devices disclosed herein provide
advantageous delivery of volatile process components to a critical
process application. In many embodiments, the methods, systems, and
devices disclosed herein are particularly applicable to hydrazine.
Certain devices disclosed herein are also applicable to other
volatile process components.
In certain embodiments, the advantageous hydrazine delivery
provided by the present invention, and specifically the methods,
systems, and devices of certain embodiments described herein, may
be obtained using a membrane contactor. In a preferred embodiment,
a non-porous membrane is employed to provide a barrier between the
hydrazine solution and the head space that is in fluid contact with
a carrier gas or vacuum. Preferably, hydrazine rapidly permeates
across the membrane, while gases are excluded from permeating
across the membrane into the solution. In some embodiments the
membrane may be chemically treated with an acid, base, or salt to
modify the properties of the membrane.
In certain embodiments, the hydrazine is introduced into a carrier
gas or vacuum through a substantially gas-impermeable ionic
exchange membrane. Gas impermeability can be determined by the
"leak rate." The term "leak rate" as used herein is a broad term,
and is to be given its ordinary and customary meaning to a person
of ordinary skill in the art (and is not to be limited to a
specialized or customized meaning), and refers without limitation
to the volume of a particular gas that penetrates the membrane
surface area per unit of time. For example, a substantially
gas-impermeable membrane could have a low leak rate of gases (e.g.,
a carrier gas) other than a process gas (e.g., hydrazine), such as
a leak rate of less than about 0.001 cm3/cm2/s under standard
atmospheric temperature and pressure. Alternatively, a
substantially gas-impermeable membrane can be identified by a ratio
of the permeability of a process gas vapor compared to the
permeability of other gases. Preferably, the substantially
gas-impermeable membrane is more permeable to such process gases
than to other gases by a ratio of at least 10,000:1, such as a
ratio of at least about 20,000:1, 30,000:1, 40,000:1, 50,000:1,
60,000:1, 70,000:1, 80,000:1, 90,000:1 or a ratio of at least
100,000:1, 200,000:1, 300,000:1, 400,000:1, 500,000:1, 600,000:1,
700,000:1, 800,000:1, 900,000:1 or even a ratio of at least about
1,000,000:1. However, in other embodiments, other ratios that are
less than 10,000:1 can be acceptable, for example 1.5:1, 2:1, 3:1,
4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1; 50:1, 100:1, 500:1, 1,000:1, or
5,000:1 or more.
In certain embodiments, the membrane is an ion exchange membrane,
such as a polymer resin containing exchangeable ions. Preferably,
the ion exchange membrane is a fluorine-containing polymer, e.g.,
polyvinylidenefluoride, polytetrafluoroethylene (PTFE), ethylene
tetrafluoride-propylene hexafluoride copolymers (FEP), ethylene
tetrafluoride-perfluoroalkoxyethylene copolymers (PFE),
polychlorotrifluoroethylene (PCTFE), ethylene tetrafluorideethylene
copolymers (ETFE), polyvinylidene fluoride, polyvinyl fluoride,
vinylidene fluoride-trifluorinated ethylene chloride copolymers,
vinylidene fluoride-propylene hexafluoride copolymers, vinylidene
fluoridepropylene hexafluoride-ethylene tetrafluoride terpolymers,
ethylene tetrafluoridepropylene rubber, and fluorinated
thermoplastic elastomers. Alternatively, the resin comprises a
composite or a mixture of polymers, or a mixture of polymers and
other components, to provide a contiguous membrane material. In
certain embodiments, the membrane material can comprise two or more
layers. The different layers can have the same or different
properties, e.g., chemical composition, porosity, permeability,
thickness, and the like. In certain embodiments, it can also be
desirable to employ a layer (e.g., a membrane) that provides
support to the filtration membrane, or possesses some other
desirable property.
The ion exchange membrane is preferably a perfluorinated ionomer
comprising a copolymer of ethylene and a vinyl monomer containing
an acid group or salts thereof. Exemplary perfluorinated ionomers
include, but are not limited to, perfluorosulfonic
acid/tetrafluoroethylene copolymers ("PFSA-TFE copolymer") and
perfluorocarboxylic acid/tetrafluoroethylene copolymer ("PFCA-TFE
copolymer"). These membranes are commercially available under the
tradenames NAFION.RTM. (E.I. du Pont de Nemours & Company), 3M
Ionomer (Minnesota Mining and Manufacturing Co.), FLEMION.RTM.
(Asashi Glass Company, Ltd.), and ACIPLEX.RTM. (Asashi Chemical
Industry Company), and Aquivon.RTM. (Solvay).
In preparing a hydrazine containing gas stream, a hydrazine
solution can be passed through the membrane. The term "passing a
hydrazine solution through a membrane" as used herein is a broad
term, and is to be given its ordinary and customary meaning to a
person of ordinary skill in the art (and is not to be limited to a
special or customized meaning), and refers without limitation to
contacting a first side of a membrane with the hydrazine solution,
such that the hydrazine passes through the membrane, and obtaining
a hydrazine containing gas stream on the opposite side of the
membrane. The first and second sides can have the form of
substantially flat, opposing planar areas, where the membrane is a
sheet. Membranes can also be provided in tubular or cylindrical
form where one surface forms the inner position of the tube and an
opposing surface lies on the outer surface. The membrane can take
any form, so long as the first surface and an opposing second
surface sandwich a bulk of the membrane material. Depending on the
processing conditions, nature of the hydrazine solution, volume of
the hydrazine solution's vapor to be generated, and other factors,
the properties of the membrane can be adjusted. Properties include,
but are not limited to physical form (e.g., thickness, surface
area, shape, length and width for sheet form, diameter if in fiber
form), configuration (flat sheet(s), spiral or rolled sheet(s),
folded or crimped sheet(s), fiber array(s)), fabrication method
(e.g., extrusion, casting from solution), presence or absence of a
support layer, presence or absence of an active layer (e.g., a
porous prefilter to adsorb particles of a particular size, a
reactive prefilter to remove impurities via chemical reaction or
bonding), and the like. It is generally preferred that the membrane
be from about 0.5 microns in thickness or less to 2000 microns in
thickness or more, preferably from about 1, 5, 10, 25, 50, 100,
200, 300, 400, or 500 microns to about 600, 700, 800, 900, 1000,
1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, or 1900 microns.
When thinner membranes are employed, it can be desirable to provide
mechanical support to the membrane (e.g., by employing a supporting
membrane, a screen or mesh, or other supporting structure), whereas
thicker membranes may be suitable for use without a support. The
surface area can be selected based on the mass of vapor to be
produced.
Certain embodiments of the methods, systems, and devices provided
herein, in which a carrier gas or vacuum can be used to deliver
substantially water-free hydrazine, are shown by reference to the
Figures.
According to certain embodiments of the present invention, a
hydrazine delivery assembly (HDA) is provided. An HDA is a device
for delivering hydrazine into a process gas stream, e.g., a carrier
gas used in a critical process application, e.g., microelectronics
manufacturing or other critical process applications. An HDA may
also operate under vacuum conditions. An HDA may have a variety of
different configurations comprising at least one membrane and at
least one vessel containing a non-aqueous hydrazine solution and a
head space separated from the solution by membrane.
FIGS. 1A and 1B depict different views of one embodiment of an HDA
100 and a membrane assembly 110 that forms part of an HDA that can
be used as provided herein. FIG. 1A shows membrane assembly 110
comprising a plurality of membranes 120, for example, 5R
NAFION.RTM. membrane, which can be configured as lumens. As
depicted in FIG. 1A, membranes 120 configured into lumens are
inserted into a collector plate 130 through a plurality of holes
within collector plate 130. Membrane assembly 110 also comprises a
plurality of polytetrafluoroethylenene (PTFE) rods 140 inserted
into collector plate 130. As shown in FIG. 1B, as part of HDA 100,
membrane assembly 110 comprises membrane lumens 120 spanning
collector plates 130. HDA 100 further comprises endcaps 150 at each
end of membrane assembly 110. Endcaps 150 further include branches
160, which can be fitted with tubing to provide access to the
interior of HDA 100, e.g., to fill, empty, clean, or refill the
HDA.
FIG. 2A and FIG. 2B show a cross-sectional view of two embodiments
of HDAs according to certain embodiments of the present
invention.
HDA 200A, as shown in FIG. 2A, comprises a membrane assembly 210A
within a shell housing 220A and end caps 230A configured to couple
to shell housing 220A. Membrane assembly 210A comprises of a
plurality of membranes 240A, which can be configured as lumens. The
number of lumens can vary depending on various factors, including
the size of the lumens, the size of HDA 200A, and the operating
conditions of the HDA. In certain embodiments, an HDA may contain
up to 1000 membrane lumens, up to 500 lumens, up to 200 lumens, up
to 100 lumens, or up to 50 lumens. For example, HDA 200A may have
about 20-50 membrane lumens. The membrane lumens can be constructed
from a perfluorinated sulfonic acid membrane, for example, 5R
NAFION.RTM. membrane. The end caps 230A and shell housing 220A can
be formed from a variety of materials, for example, PTFE, stainless
steel (such as 316 stainless steel), or other suitable materials.
Each end cap 230A further comprises a gas connection 231A. Gas
connection 231A can take the form of a variety of connection
configurations and sizes, for example, 1/4'' VCR, 1/4'' NPT, or
other suitable connectors.
HDA 200B, as shown in FIG. 2B, comprises a membrane assembly 2108
within a shell housing 220B and end caps 230B configured to couple
to shell housing 220B. Membrane assembly 210B can be comprised of a
plurality of membrane lumens (not shown). The number of lumens can
vary depending on various factors, including the size of the
lumens, the size of HDA 200B, and the operating conditions of the
HDA. In certain embodiments, an HDA may contain up to 1000 membrane
lumens, up to 500 lumens, up to 200 lumens, up to 100 lumens, or up
to 50 lumens. For example, HDA 200B may have about 20-50 membrane
lumens. The membrane lumens can be constructed from a
perfluorinated sulfonic acid membrane, for example, 5R NAFION.RTM.
membrane. The end caps 230B and shell housing 220B can be formed
from a variety of materials, for example, PTFE, stainless steel
(such as 316 stainless steel), or other suitable materials. Each
end cap 230B can comprise a gas connection 231B. Gas connection
2318 can take the form of a variety of connection configurations
and sizes, for example, 1/4'' VCR, 1/4'' NPT, or other suitable
connectors.
According to the various embodiments, the HDA can be filled with a
non-aqueous hydrazine containing solution, while maintaining a head
separated from the hydrazine containing solution by a membrane.
Because the membrane is permeable to hydrazine and substantially
impermeable to the other components of the solution, the head space
will contain substantially pure hydrazine vapor in a carrier gas or
vacuum, depending upon the operating conditions of the process.
According to various embodiments, an HDA can be constructed
similarly to the devices described in commonly assigned U.S. Pat.
No. 7,618,027, which is herein incorporated by reference.
According to certain embodiments, a device for containing liquid
and a vapor phase comprising a volatile chemical or composition,
which may be a non-aqueous hydrazine containing solution, is
provided, wherein the membrane contacts the volatile chemical or
composition on one side of the membrane and a carrier gas stream on
the other side of the membrane. FIG. 12 depicts one example of such
a device 1200, comprising (a) a chamber containing a liquid
comprising a volatile chemical or chemical composition, (b) a head
space comprising a vapor phase that includes the volatile chemical
or chemical composition in the gas phase, (c) a inlet port through
which a carrier gas stream can enter the chamber, and (d) a
protected outlet port through which a process gas stream comprising
carrier gas and the volatile chemical or chemical composition can
exit the head space.
As shown in FIG. 12, carrier gas 1214 enters through the inlet port
1202. Carrier gas 1214 then moves through the membrane 1208 which
is attached to inlet port 1202 by seal 1216. In certain
embodiments, seal 1216 provides a leak tight connection between
inlet port 1202 and 1208. In certain embodiments, seal 1216 may not
be leak tight or may be a partial seal to allow a portion of
carrier gas 1214 to flow into head space 1210. In certain
embodiments, membrane 1208 is a tubular membrane, but the geometry
of the may be adapted according to the requirements of the
particular application or process in which the device is used. One
side of membrane 1208 is configured to contact liquid 1212, which
comprises a volatile chemical or composition capable of diffusing
across membrane 1208. Carrier gas 1214 flows through membrane 1208
on a side opposite the side that is in contact with liquid 1212.
Process gas stream 1218, comprising the volatile chemical or
composition in the gas phase, is formed as the volatile chemical or
composition diffuses across the membrane into the carrier gas
stream. Membrane 1208 allows certain components of liquid 1212 to
diffuse across the membrane into the carrier gas stream to provide
a select process gas stream 1218, while preventing other components
of liquid 1212 from diffusing into the process gas stream 1218
(e.g., water, metal ions, other ionic contaminants, and other
contaminants). At the outlet 1222 of membrane 1208, process gas
stream 1218, comprising carrier gas 1214 and a process chemical
from liquid 1212, enters headspace 1210. Thus, the pressure inside
of tubular membrane 1208 matches the pressure in head space 1210
and, thus, the vapor pressure of liquid 1212, which prevents the
collapse of the membrane when the outlet pressure is lower than the
inlet pressure. Process gas 1220 contained in headspace 1210 exits
the device through the splash guard 1206 and outlet port 1204 for
delivery to a critical process 1224. In this embodiment, splash
guard 1206 retains the open end 1222 of the tubular membrane 1208
such that the process gas stream exiting passing through outlet
port 1204 is substantially free of liquid contaminants, e.g.,
droplets, particles, mists, or fogs.
In many embodiments, e.g., the embodiment shown in FIG. 12, the
membrane is partially immersed in the liquid source. Submerging the
membrane increases the mass transfer surface area and the residence
time the carrier gas has to fully saturate with gas generated from
the liquid source. The membrane may be long enough to reach the
bottom of the canister and then back up to the surface above the
liquid. The membrane can range from about 3.0 inches in length or
less to about 72 inches in length or more, including lengths in
between such as about 5, 10, 15, 20, 25, 30, or 35 inches to about
40, 45, 50, 55, 60, or 65 inches or more. The immersed part of the
membrane can be coiled to increase liquid to membrane surface area.
Multiple membranes can be used and run in parallel to further
increase liquid to membrane surface area. The membrane may be about
0.002 inches thick or less to about 0.010 inches thick or more,
including about 0.003, 0.004, or 0.005 inches thick to about 0.006,
0.007, 0.008, or 0.009 inches thick or more. The diameter of the
membrane may be about 0.062 inches or less to about 0.250 inches or
more, including 0.070, 0.080, 0.090, 0.100, 0.110, 0.120, 0.130,
0.140, or 0.150 inches to about 0.160, 0.170, 0.180, 0.190, 0.200,
0.210, 0.220, 0.230, or 0.240 inches or more.
In many embodiments, e.g., the embodiment shown in FIG. 12, the
device includes a splash guard. The splash guard limits the volume,
velocity, or nature of the liquid exiting through the outlet of the
device. The splash guard is capable of maintaining the outlet of
the tubular membrane above the liquid. In several embodiments, the
splash guard has a long narrow slit in the conductive path to the
outlet barb which prevents droplets from entering the gas stream
leaving the outlet port. The splash guard is made of a material
compatible with the chemistries being used in the liquid source and
carrier gas. For example, low-reactive materials such as, but not
limited to, stainless steel, aluminum, or plastic may be used. The
splash guard may be attached to the container by fitting onto the
outlet barb. In some embodiments, the splash guard is about 1.50
inches in height, the slit is about 0.03 inches in width and about
1.25 inches in height, and the slit's length is the same as the
diameter of the splash guard which is about 1.00 inch.
Although a primary purpose of the present disclosure is gas phase
delivery of non-aqueous hydrazine according the methods, systems,
and devices provided herein, other process chemicals capable of
diffusing across the membrane may be used in the liquid source and,
therefore, may also be part of process gas stream 1218 exiting the
outlet port, include hydrogen peroxide, water, alcohols (such as
ethanol, methanol, ethylene glycol, pentanol, glycerol, xylitol, or
isopropyl alcohol), amines (such as hydrazine, methylamine,
ethanolamine, dimethylamine, aniline, trimethylamine,
triphenylamine, aziridine, or methylethanolamine), or ammonium
hydroxide. These process chemicals, whether in the liquid source or
in the process gas, may be used alone or in combination. In certain
embodiments, the liquid source may include a polar solvent, whereas
in certain other embodiments the liquid source may include a
nonpolar solvent.
The devices disclosed herein that are capable of containing a
liquid source comprising at least one process chemical and
delivering at least one process chemical in the gas phase to a
critical process application, e.g., the device shown in FIG. 12,
may be used in conjunction with the methods, systems, and other
devices of the present invention, or they may be used as standalone
devices for delivering a process gas stream to a critical process
application.
An embodiment according to an aspect of the methods, systems, and
devices provided herein is described below by reference to a
manifold 300, as shown by reference to FIG. 3. According to the
embodiment shown by reference to FIG. 3, a carrier gas 310 flows
through the head space of HDA 320, which can be an HDA as described
above. A mass flow controller (MFC) 330, for example, Unit
UFC-1260A 1 slm, can be used to control the flow rate of carrier
gas 310, which can be set to 1 slm, for example. Analysis of the
amount of hydrazine in the gas stream may require dilution of the
resultant gas stream, which can be accomplished with dilution gas
350. A mass flow controller (MFC) 340, for example, a Unit
UFC-1260A 10 slm can be used to control the flow rate of dilution
gas 350. Carrier gas 310 and dilution gas 350 can be supplied by a
gas source 360, which can be typically nitrogen or other suitable
carrier gas. A valve 370 can be used to isolate the dilution line
when it is not required. Check valves 371, 372 can be placed
downstream of both MFC 330 and MFC 340 to protect them from
possible hydrazine exposure. A 60 psig pressure gauge 373 can be
placed between MFC 330 and check valve 372 to insure that the
manifold's pressure does not exceed the maximum pressure allowed by
hydrazine analyzer 380, e.g., 5 psig.
The nitrogen pressure can be maintained with a forward pressure
regulator 374, typically set to 15 psig. A thermocouple 375 can
measure the temperature of nitrogen carrier gas 310 before it
enters HDA 320 for hydrazine addition. A thermocouple 376 can
measure the temperature of the hydrazine solution in HDA 100. A
thermocouple 377 can measure the gas temperature before entering
hydrazine analyzer 380. Hydrazine analyzer 380 can pull in a sample
of carrier gas 310 to measure the hydrazine concentration. Manifold
300 can further comprise a relative humidity/resistance temperature
detector (RH/RTD) probe 378. A heater tape 390 can be placed on
certain sections as indicated in FIG. 3. The manifold's temperature
can be controlled in two separate zones, the membrane assemblies
and the remaining tubing, with a Trilite Equipment &
Technologies Controller and a Watlow 96 Controller, respectively.
The entire manifold can be set up inside of a fume hood.
The embodiment shown by reference to FIG. 3 is set up as a test
apparatus to measure the amount of hydrazine introduced into a
carrier gas stream under various operating conditions of an HDA. It
will be understood that a similar apparatus can be used to deliver
hydrazine to a critical process application.
FIG. 4 is a P&ID of a test manifold 400, according to another
embodiment, used to demonstrate delivery of hydrazine under vacuum
conditions, according to the methods, systems, and devices provided
herein. According to the embodiment shown by reference to FIG. 4, a
vacuum pump 410 removes gas from the hydrazine containing vapor
side (i.e., head space) of HDA 420, which can be an HDA as
described above. For example, vacuum pump 410 can be maintained at
about 24 mmHg using a valve 480 and a pressure gauge 430. A gas
source 440 can be maintained at a pressure of about 2 psig with a
forward pressure regulator 450. A valve 460 can be used as a flow
restrictor. A thermocouple 470 can be placed inside the filling
tube of a HDA 420 to measure the solution's temperature inside the
shell of HDA 420. The test involves contacting the vapor side,
i.e., head space, of HDA 420 to a vacuum produced by vacuum pump
410 while holding HDA 420 at a constant temperature. A heat tape
490 can be placed around HDA 420 to allow for constant temperature
control of the hydrazine containing solution within HDA 420. This
vacuum-based method, system, and device is particularly preferred
in numerous micro-electronics and other critical process
applications that are operated at relatively reduced pressures
(i.e., under vacuum).
The embodiment shown by reference to FIG. 4 is set up as a test
apparatus to measure the amount of hydrazine introduced into a
carrier gas stream under various operating conditions of an HDA. It
will be understood that a similar apparatus can be used to deliver
hydrazine to a critical process application.
FIG. 5 is a P&ID of a test manifold 500, according to another
embodiment, used to demonstrate delivery of hydrazine, according to
an aspect of the methods, systems, and devices provided herein. As
shown in FIG. 5, a nitrogen carrier gas 510 can flow through the
head space of HDA 520, which can be an HDA as described above. A
mass flow controller (MFC) 530, for example, a Brooks
SLA5850S1EAB1B2A1 5 slm, can be used to control the flow rate of
nitrogen carrier gas 510, which can be set to 1 slm, for example.
Analysis of the amount of hydrazine in the gas stream may require
dilution of the resultant gas stream, which can be accomplished
with dilution gas 550. A mass flow controller (MFC) 540, for
example, a Brooks SLA5850S1EAB1B2A1 10 slm, can be used to control
the flow rate of a nitrogen dilution gas 550. Nitrogen carrier gas
510 and nitrogen dilution gas 550 can be supplied by a nitrogen gas
source 560. A valve 570 can be used to isolate the dilution line
when desired. A pair of check valves 571, 572 can be placed
downstream of both MFC 530 and MFC 540 to protect them from
possible hydrazine exposure. A pressure gauge 573, for example, 100
psi gauge, can be placed between MFC 530 and HDA 520 to insure that
the manifold's pressure does not exceed any maximum pressure
allowed by an analyzer 580.
The nitrogen pressure can be maintained with a forward pressure
regulator 574, for example set to 25 psig. A thermocouple 575 can
measure the temperature of nitrogen carrier gas 510 before it
enters HDA 520 for hydrazine addition. Within HDA 520, nitrogen
carrier gas 510 can flow through the membrane tubes and hydrazine
vapor can permeate through the membrane from the solution contained
within the shell housing and combined with carrier gas 510. A
thermocouple 576 can measure the temperature of the hydrazine
solution in HDA 520. A thermocouple 577 can measure the gas
temperature exiting HDA 520. In this embodiment, an analyzer 580
can be used to measure the hydrazine concentration in the gas
stream. Analyzer 580 can be, for example, a MiniRAE 3000, which has
a photoionization detector with an 11.7 eV gas discharge lamp.
Analyzer 580 can, for example, pull a sample of the hydrazine
containing gas stream to measure the hydrazine concentration. A
thermocouple 578 can be used to measure the gas temperature before
entering analyzer 580. A thermocouple 581 can be used to measure
the temperature of nitrogen dilution gas 550.
Manifold 500 can further comprise a catalytic converter 585
configured to remove the hydrazine by converting it into nitrogen
and hydrogen. Downstream of catalytic converter 585 can be a probe
579, for example, a E+E Elektronik EE371 humidity transmitter
configured to measure the dew point (DP) and moisture
concentration. Downstream of probe 579 can be a vent. A heater tape
590 can be placed on certain sections as indicated in FIG. 5. The
manifold's temperature can be controlled in four separate zones,
indicated by the dotted line boxes, with Watlow EZZone.RTM. 96
controllers, respectively. The entire manifold can be set up inside
of a fume hood.
The embodiment shown by reference to FIG. 5 is set up as a test
apparatus to measure the amount of hydrazine introduced into a
carrier gas stream under various operating conditions of an HDA. It
will be understood that a similar apparatus can be used to deliver
hydrazine to a critical process application.
FIG. 6 is a diagram illustrating a cross-section of a membrane
assembly useful in certain embodiments of the present invention
when a single membrane is used. The membrane assembly may be
incorporated into, for example, an HDA such as one shown in FIG.
1B. As shown in FIG. 6, in one embodiment of the invention, the
membrane may be a single membrane lumen sleeved over a stainless
steel tube containing a calibrated number of holes to provide a
specific membrane surface area available for permeation. The
sleeved stainless steel tube is encased inside an outer tube to
form the Hydrazine Delivery Assembly (HDA). Liquid hydrazine is
filled inside the space between the inner and outer tubes. A
carrier gas is directed to flow through the inner tube to carry
hydrazine vapor which has permeated the membrane to the desired
process.
FIG. 7 is a P&ID of a manifold that can be used to test
methods, systems, and devices for hydrazine delivery according to
certain embodiments of the present invention. According to this
embodiment, a carrier gas (CG) flows through the head space of the
HDA, labeled "Vaporizer," which can be an HDA as described above. A
mass flow controller (MFC 1), for example, a 5 slm Brook's
SLA5850S1EAB1B2A1 mass flow controller, can be used to control the
flow rate of carrier gas into the HDA. Analysis of the amount of
hydrazine in the gas stream exiting the vaporizer may involve first
diluting the resultant gas stream, which can be accomplished with a
dilution gas (DG-1). A mass flow controller (MFC 2), for example, a
10 slm Brook's SLA5850S1EAB1B2A1 mass flow controller, can be used
to control the flow rate of dilution gas DG-1. A separate line of
dilution gas DG-2 may be supplied to a portion of the manifold
positioned within a Glove Bag.
Carrier gas CG and dilution gases DG-1 and DG-2 can be supplied by
a Gas Source, which can be typically nitrogen or other suitable
carrier gas. In some embodiments such as the one shown in FIG. 7,
the carrier gas and dilution gases share the same gas source. In
other embodiments, the carrier gas and dilution gases may have
independent gas sources. Valves V-1 and V-2 can be used to control
gas flow into the HDA/DG-1 dilution line or into the DG-2 dilution
line/Glove Bag, respectively. Check valves CV-1 and CV-2 can be
placed downstream of MFC 2 and MFC 1, respectively, to protect them
from possible hydrazine exposure. A pressure gauge PG-2 can be
placed between CV-2 and the Vaporizer to measure pressure upstream
of the Vaporizer.
The carrier gas pressure can be maintained with a forward pressure
regulator PR1 and measured with pressure gauge PG-1. A forward
pressure regulator PR2 can be used to control the flow of dilution
gas DG-2 through the Gas Bag. A thermocouple T-1 can measure the
temperature of the hydrazine solution in the Vaporizer. A
thermocouple T-2 can measure the gas temperature after a mixing
loop and before entering a hydrazine analyzer. The MiniRAE 3000 is
one example of a hydrazine analyzer. Heater tape HT can be placed
on certain sections, such as on the Vaporizer, a portion of the
dilution gas DG-1 line, and lines downstream of the Vaporizer as
indicated in FIG. 7. The manifold may also comprise catalytic
converters downstream of the Vaporizer and Glove Bag to decompose
hydrazine to nitrogen and hydrogen. The entire manifold can be set
up inside of a fume hood.
The embodiment shown by reference to FIG. 7 is set up as a test
apparatus to measure the amount of hydrazine introduced into a
carrier gas stream under various operating conditions of an HDA. It
will be understood that a similar apparatus can be used to deliver
hydrazine to a critical process application.
Example 1
Experimental
In the examples of the disclosure, membranes were prepared by
purchasing sulfonyl fluoride perfluorinated polymers, extruding
them, and then hydrolyzing them by methods known in the art to form
membranes. Such membranes are also referred to as NAFION.RTM.
herein.
The manifold illustrated in FIG. 7 was utilized for a test
procedure in this Example. The test procedure involved obtaining
stable gas phase hydrazine readings utilizing a non-aqueous,
substantially pure hydrazine solvent as a liquid source.
A NAFION.RTM. vaporizer (P/N#200801-01) was used for this
experiment. This vaporizer included a single 5R NAFION.RTM.
membrane sleeved over a 1/8'' SS (stainless steel) tubing. The SS
tubing had twenty 0.06'' diameter holes, allowing for a total
permeable area of 0.06 in.sup.2. The tubing was enclosed by a 3/8''
SS tubing with two 1/4'' fill ports for the shell side. The volume
of the shell side was approximately 8 ml.
The manifold was setup in a fume hood. The nitrogen pressure was
maintained at 25 psig with a forward pressure regulator (PR-1) and
measured with a pressure gauge (PG-1). Two valves (V-1 and V-2)
were used to terminate gas flow through vaporizer and/or dilution
line. A 5 slm Brook's SLA5850S1EAB1B2A1 Mass Flow Controller
(MFC-1) was used to control the carrier gas flow rate. A 10 slm
Brook's SLA5850S1EAB1B2A1 Mass Flow Controller (MFC-2) was used to
control the dilution gas flow rate. Check valves (CV-1 and CV-2)
were placed downstream of both MFCs to protect them from being
exposed to hydrazine. A forward pressure regulator with gauge
(PR-2) was used to control flow of nitrogen through gas bag. The
pressure upstream of the vaporizer was measured with a pressure
gauge (PG-2). A J-type thermocouple (TC-1) was attached to the
vaporizer as a control point for the heater tape. The carrier gas
was mixed with the nitrogen from the dilution line downstream of
the vaporizer. A J-type thermocouple (TC-2) was used to monitor gas
temperature after mixing. A MiniRAE 3000, which has a
photoionization detector (PID) with an 11.7 eV gas discharge lamp,
was used to measure the hydrazine concentration in the gas stream.
The test manifold and glove bag vent lines had catalytic converters
that decomposed the hydrazine to nitrogen and hydrogen. The
vaporizer, a portion of the dilution line, and the test manifold
downstream of the vaporizer was heat-traced with heater tape.
For this experiment, the carrier gas flow was set to 1 slm. The
dilution gas flow was initially set to 1 slm and would be increased
if the concentration was above 2000 ppm (upper detection limit of
the MiniRae 3000). The manifold was heated to keep the gas
temperature at 30.degree. C. at TC-2.
FIG. 8 represents the results from this experiment with the carrier
gas flow and dilution gas flow at 1 slm. As shown, the hydrazine
output was directly affected by the gas temperature once the system
was stabilized. This effect was demonstrated when the temperature
setpoint for this experiment was raised from 30.degree. C. to
31.degree. C. 78 minutes into the test. The average concentration
of hydrazine was 2426 ppm for the last 26 minutes of the test. The
result is a permeation rate of 0.04043 L/min/in.sup.2 under these
conditions.
Example 2
The manifold illustrated in FIG. 9 was utilized for test procedures
in this Example. The test procedures involved obtaining stable gas
phase hydrazine readings using either an anhydrous 98% hydrazine
solvent as a liquid source, or a solution of 65% hydrazine in
poly(ethylene glycol) dimethyl ether solvent (Mn=250) as a liquid
source.
A NAFION.RTM. vaporizer (P/N#200846-A) was used for these
experiments. This vaporizer consisted of a single 5R NAFION.RTM.
membrane sleeved over a 1/8'' SS tubing. The SS tubing had ten
0.06'' diameter holes, allowing for a total permeable area of 0.03
in.sup.2. The tubing is enclosed by a 3/8'' SS tubing with two
1/4'' fill ports for the shell side. The volume of the shell side
was approximately 8 ml.
The manifold was setup in a fume hood. An Entegris 500KF Gatekeeper
purifier was used to remove oxygen, water, and hydrocarbons from
the gas stream. Two valves (V-1 and V-2) were used to terminate gas
flow through glove box and the test manifold respectively. The
nitrogen flow inside the glove box was maintained with a forward
pressure regulator and the pressure measured with a pressure gauge
(PG-1). A check valve (CV-1) was placed upstream of the glove box
to prevent back streaming of the hydrazine. A forward pressure
regulator with gauge was used to maintain a gas pressure of 25 psig
upstream of the MFCs. A 5 slm Brook's SLA5850S1EAB1B2A1 Mass Flow
Controller (MFC-1) was used to control the carrier gas flow rate. A
10 slm Unit Mass Flow Controller (MFC-2) was use to control the
dilution gas flow rate. Check valves (CV-2 and CV-3) were placed
downstream of both MFCs to protect them from being exposed to
hydrazine.
A single-lumen vaporizer was used to add hydrazine vapor to the gas
stream. The mixing loop was used to mix nitrogen from the dilution
line and hydrazine vapor in the carrier gas downstream of the
vaporizer. A J-type thermocouple (TC-1) was used to monitor gas
temperature after mixing. A MiniRAE 3000, which has a
photoionization detector (PID) with an 11.7 eV gas discharge lamp,
was used to measure the hydrazine concentration in the gas stream.
The test manifold and glove box vent lines had scrubbers that
catalytically decompose the hydrazine to nitrogen and hydrogen. A
valve (V-3) was used to create backpressure in the glove box and
for isolation.
For this Example, two solutions were tested at room temperature.
One solution was anhydrous 98% hydrazine (Sigma Aldrich). The
second solution was 65% w/w hydrazine (.rho.=1.029 g/ml) in
poly(ethylene glycol) dimethyl ether (.rho.=1.03 g/ml). An 8 ml
solution was made with 5.2 ml of anhydrous 98% hydrazine and 2.8 ml
of poly(ethylene glycol) dimethyl ether.
Before each test run, the MiniRAE 3000 was calibrated with 100 ppm
isobutene gas standard. Once the analyzer was attached the test
manifold, the solution was added to the vaporizer without gas
flowing through the test manifold. Once filled, the carrier gas
flow was set to 1 slm and the dilution gas flow was to 1 slm. The
dilution gas flow would be increased if the concentration was above
2000 ppm (upper detection limit of the MiniRAE 3000). Readings of
the gas temperature and hydrazine concentration were recorded.
Stabilization would be determined as when the vaporizer output
change was less than 5 ppm/min.
FIG. 10 represents the results from the anhydrous 98% hydrazine
with the carrier gas flow and dilution gas flow at 1 slm for 330
minutes. After stabilization was reached in ten minutes, the
average concentration was 1482.7 ppm.+-.102.2 ppm at an average
temperature of 23.6.degree. C..+-.0.4.degree. C. Thus, the
concentration was stable to within less than 10% of the average
concentration. The result is an average permeation rate of 0.04942
L/min/in.sup.2 under these conditions. This hydrazine permeation
rate was close to the 0.04043 L/min/in.sup.2 permeation rate
measured during the previous test done in Example 1.
FIG. 11 represents the results from the 65% hydrazine in
poly(ethylene glycol) dimethyl ether with the carrier gas flow and
dilution gas flow at 1 slm for 320 minutes. After stabilization was
reached in 30 minutes, the average concentration was 1190.6
ppm.+-.27.6 ppm with an average temperature of 24.5.degree.
C..+-.0.3.degree. C. The result was an average permeation rate of
0.03969 L/min/in.sup.2 under these conditions. Spikes in hydrazine
concentration shown near time zero in FIGS. 10 and 11 reflect
artifacts in the measuring instruments and are not deemed to be
accurate or relevant.
The permeation was 19.7% less with the 65% hydrazine/poly(ethylene
glycol) dimethyl ether solution in comparison to the 98% hydrazine
solution. An encouraging attribute shown with the 65%
hydrazine/solvent was that the output was more stable over time
than the 98% hydrazine hydrate solution. In 290 minutes the 98%
hydrazine solution concentration output decreased 263 ppm. However,
the 65% hydrazine/poly(ethylene glycol) dimethyl ether solution
concentration output only decreased 23 ppm in 290 minutes. The
overall result with the poly(ethylene glycol) dimethyl ether
presents it as a viable solvent for safe hydrazine vapor
delivery.
By controlling the temperature of the hydrazine containing solution
and, as applicable, the carrier gas or vacuum, particular hydrazine
concentrations can be delivered The stability of the hydrazine
concentration in the process gas stream can be controlled to less
than about 20%, e.g., less than about 18%, less than about 16%,
less than about 14%, or less than about 12%, or less than about
10%. In a preferred embodiment, the stability of the hydrazine
concentration in the process gas stream can be controlled to less
than about 10% of the average concentration within one standard
deviation, e.g., less than about 9%, less than about 8%, less than
about 7%, less than about 6%, less than about 5%, less than about
4%, less than about 3%, less than about 2%, or even less than about
1%. The average concentration does not include measurements by the
instrument prior to achieving equilibrium. For example, the
measurement in FIG. 11 of hydrazine concentration includes what
appears to be a spike of up to about 1900 ppm. This spike is an
instrument factor and not an actual measurement as it takes on the
order of about 10 minutes or more for the instrument to stabilize
and all average concentration readings hereunder take such
stabilization into account. The selection of a particular hydrazine
concentration will depend on the requirements of the application or
process in which the hydrazine containing process gas will be used.
In certain embodiments, the hydrazine containing gas stream may be
diluted by adding additional carrier gas. In certain embodiments,
the hydrazine containing gas stream may be combined with other
process gas streams prior to or at the time of delivering hydrazine
to an application or process. Alternatively or additionally, any
residual solvent or stabilizers, or contaminants present in the
hydrazine containing process gas may be removed in a purification
(e.g., dehumidification) step using a purifier apparatus.
Example 3
The manifold illustrated in FIG. 13 was utilized for test
procedures in this Example. The Brute.TM. vaporizer 1306 was
assembled with a PTFE splash guard on the outlet barb and a new
lumen assembly. Brute.TM. vaporizer 1306 was filled with 200 mL of
a liquid source solution comprising hydrogen peroxide and the lid
was assembled. The test system 1300 was assembled as shown in FIG.
13. Manometer 1310 was connected to the display readout. All valves
1302, 1304, 1308, and 1312 were closed and vacuum pumps 1318, 1320,
and 1322 were off. Cold trap bath 1316 was filled with liquid
nitrogen. Outlet back pressure valve (BPV) 1304 was closed and
valve 1312 was opened. Vacuum pumps 1318, 1320, and 1322 were
turned on, the cold trap bath 1316 was opened, and the equilibrium
pressure was recorded. Outlet BPV 1304 was quickly opened to shock
vaporizer 1306 with low pressure. Observation perfluoroalkoxy (PFA)
Tube 1324 was monitored for signs of droplets of the liquid source
solution. Vaporizer 1306 was exposed to vacuum until the pressure
was constant. Valve 1312 was turned off and the rate of rise was
recorded in minute intervals. The test was repeated several times.
The splash guard prevented liquid solution from entering the outlet
of vaporizer 1306 at pressures below 1 torr.
Other embodiments of the invention will be apparent to those
skilled in the art from consideration of the specification and
practice of the invention disclosed herein. It is intended that the
specification and examples be considered as exemplary only, with a
true scope and spirit of the invention being indicated by the
following claims.
* * * * *